EP0002077B1 - Esters of substituted cyclopropanecarboxylic acids and process for the preparation thereof - Google Patents

Esters of substituted cyclopropanecarboxylic acids and process for the preparation thereof Download PDF

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Publication number
EP0002077B1
EP0002077B1 EP78200248A EP78200248A EP0002077B1 EP 0002077 B1 EP0002077 B1 EP 0002077B1 EP 78200248 A EP78200248 A EP 78200248A EP 78200248 A EP78200248 A EP 78200248A EP 0002077 B1 EP0002077 B1 EP 0002077B1
Authority
EP
European Patent Office
Prior art keywords
group
carbon atoms
hydrogen atom
dichlorovinyl
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78200248A
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German (de)
English (en)
French (fr)
Other versions
EP0002077A1 (en
Inventor
Johannes Leopold Marie Syrier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP0002077A1 publication Critical patent/EP0002077A1/en
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Publication of EP0002077B1 publication Critical patent/EP0002077B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
    • C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • This invention relates to a process for the preparation of esters of substituted cyclopropanecarboxylic acids and to the novel esters produced thereby.
  • Substituted cyclopropanecarboxylic acids are useful intermediates in the preparation of pesticidally-active esters thereof, especially the 3-phenoxybenzyl and a/pha-cyano-3-phenoxybenzyl esters; these pesticidally active compounds, the so-called “synthetic pyrethroids", have exceptionally good insecticidal properties whilst possessing a very low mammalian toxicity, see British Patent Specifications 1,413,491 and 1,446,304.
  • the present invention therefore, provides a process for the manufacture of an ester having the following general formula: (wherein each of R' and R 2 independently represents an alkyl group of 1 to 4 carbon atoms or R' and R 2 together represent an alkylene group of up to 5 carbon atoms, other than methylene, each of X l and X 2 independently represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, a halogen atom, or X I and X 2 together represent an alkylene group of up to 5 carbon atoms, other than methylene, or X' represents a hydrogen atom and X 2 a 2-halovinyl group, a 2,2-dihalovinyl group or a 2-methyl-1-propenyl group, and R represents a 2-methoxyethyl or a 2-ethoxyethyl group), which process comprises reacting a substituted cyclopropanecarbonitrile having the general formula:- wherein R 1 ,R 2 ,
  • the reaction temperature in the process according to the invention is maintained in the range 80°C to 200°C and particularly in the range 100 to 150°C.
  • the reaction conditions employed allow the use of atmospheric pressure.
  • the mineral acid is preferably concentrated sulphuric acid as this gives rise to better yields of the ester of formula I..
  • substantially anhydrous conditions that is to say, conditions under which the amount of water present during the reaction is kept to a minimum for example, below about 5% by weight of the reaction mixture, preferably below 1% and suitably below 0.5% by weight of the reaction mixture.
  • the reaction will tolerate the water normally present in concentrated sulphuric acid (2% by weight) at the concentrations of acid employed in the process, provided that the alcohol and the nitrile reactants are substantially dry.
  • the amount of mineral acid (based on the nitrile present in the process according to the invention) should lie in the range of from 3:1 to 1:1 by weight.
  • R I and R 2 preferably represent methyl groups; X, and X 2 represent chlorine or bromine atoms or methyl groups; or X l represents a hydrogen atom and X 2 a 2,2-dichlorovinyl group, a 2,2-dibromovinyl group, a 2,2-difluorovinyl group, a 2-chloro-2-fluorovinyl group, or a 2-methyl-1-propenyl group; and R represents a 2-methoxyethyl group.
  • the alcoholysis reaction enables a cyclopropanecarbonitrile to be converted into the corresponding 2-methoxyethyl or 2-ethoxyethyl ester.
  • some 3,6-dioxaheptyl (when methoxyethanol has been used) or 3,6-dioxaoctyl (when ethoxyethanol has been used) ester of the corresponding substituted cyclopropanecarboxylic acid is formed (these esters are novel compounds), together with a very small amount of an unidentified ester of the corresponding substituted cyclopropanecarboxylic acid.
  • the selectivity to the 2-methoxyethyl ester or the 2- ethoxyethyl ester is usually higher than 80% and the total of the selectivities to the three esters formed is usually higher than 95%.
  • the expression "selectivity to a certain compound", given in a percentage, is defined as: wherein a is the amount of the starting nitrile converted into that certain compound and b is the amount of the converted starting nitrile.
  • the ester of formula I may be isolated from the reaction mixture obtained by addition of water, extraction of the product obtained with an organic solvent, washing of the organic extract phase with alkaline-reacting water and evaporation of the solvent from the washed organic phase.
  • the residue thus obtained also contains the 3,6-dioxaheptyl ester or the 3,6-dioxaoctyl ester, the unidentified ester mentioned hereinbefore and 2,5,8-trioxanonane (the ether derived from methoxyethanol) or 3,6,9- trioxaundecane (the ether derived from ethoxyethanol).
  • the three esters present in the residue may then be converted to a "synthetic pyrethroid" via the free acid or the acid chloride by reaction with 3-phenoxybenzyl alcohol or a/pha-cyano-3-phenoxybenzyl alcohol.
  • the following nitriles are the most important in that they are intermediates for the pyrethroids of greatest pesticidal activity:-
  • esters of substituted cyclopropanecarboxylic acids referred to hereinbefore are esters of the general formula:- wherein

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP78200248A 1977-10-27 1978-10-17 Esters of substituted cyclopropanecarboxylic acids and process for the preparation thereof Expired EP0002077B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB4477477 1977-10-27
GB4477477 1977-10-27

Publications (2)

Publication Number Publication Date
EP0002077A1 EP0002077A1 (en) 1979-05-30
EP0002077B1 true EP0002077B1 (en) 1981-09-02

Family

ID=10434685

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78200248A Expired EP0002077B1 (en) 1977-10-27 1978-10-17 Esters of substituted cyclopropanecarboxylic acids and process for the preparation thereof

Country Status (8)

Country Link
EP (1) EP0002077B1 (da)
JP (1) JPS5470243A (da)
BR (1) BR7807041A (da)
CA (1) CA1127658A (da)
DE (1) DE2861022D1 (da)
DK (1) DK475178A (da)
IE (1) IE47464B1 (da)
IT (1) IT7829120A0 (da)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4839279A (en) * 1978-07-18 1980-01-24 Imperial Chemical Industries Ltd. Cyclopropane carboxylic acids
DE3026093C2 (de) * 1980-07-10 1983-02-10 Degussa Ag, 6000 Frankfurt 1-Methyl-2-chlorcyclopropancarbonsäure und deren verzweigte und unverzweigte C↓1↓ bis C↓6↓-Alkylester, sowie Verfahren zu deren Herstellung
DE3740840A1 (de) * 1987-11-27 1989-06-08 Schering Ag 2,2-difluorcyclopropylethanderivate, verfahren zu ihrer herstellung und ihre verwendung als schaedlingsbekaempfungsmittel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2213013B1 (da) * 1972-11-10 1976-08-20 Roussel Uclaf
GB1553818A (en) * 1975-07-24 1979-10-10 Nat Res Dev Synthesis of cyclopropane carboxylic acids
NZ185635A (en) * 1976-11-18 1980-04-28 Ici Ltd Preparation of 3-dihalovinyl-2,2-dimethylcyclopropane carboxylic acid derivatives

Also Published As

Publication number Publication date
DK475178A (da) 1979-04-28
BR7807041A (pt) 1979-05-08
EP0002077A1 (en) 1979-05-30
DE2861022D1 (en) 1981-11-26
IE47464B1 (en) 1984-03-21
CA1127658A (en) 1982-07-13
IT7829120A0 (it) 1978-10-25
IE782107L (en) 1979-04-27
JPS5470243A (en) 1979-06-05

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